1:2 Chromium complexes of disazo compounds

ABSTRACT

Complexes of the formula ##STR1## in which each of X 1  and X 2 , independently, is --COO-- or --O--, 
     each of B 1  and B 2 , independently, is the radical of a coupling component of the benzene series containing up to two non-condensed benzene rings or a radical of a coupling component of the quinoline series, which coupling component radicals are free from acid groups, 
     each of ##STR2##  independently, is the radical of a diazo component of the benzene series in which the rings A 1  and A 2  shown are free from acid groups bound directly thereto, 
     each of the floating sulpho groups on the naphthalene rings, independently, is in the 3- or 4-position, which complexes are free from fibre reactive groups and are in free acid or salt form, and mixtures of such complexes are useful as anionic dyestuffs for substrates comprising or consisting of, for example, natural or regenerated cellulose, natural or synthetic polyamides, leather, polyurethanes or polymers modified to contain basic groups.

The present invention relates to 1:2 chromium complexes of disazo compounds, their production and use as anionic dyestuffs.

Accordingly, the present invention provides 1:2 chromium complexes of disazo compounds of formula 1 ##STR3## in which each of X₁ and X₂, independently, is --COO-- or --O--,

each of B₁ and B₂, independently, is a radical of a coupling component of the benzene series containing up to two non-condensed phenyl rings or a radical of a coupling component of the quinoline series, which coupling component radicals are free from acid groups,

each of ##STR4## independently, is a radical of a diazo component of the benzene series in which the rings A₁ and A₂ shown are free from acid groups bound directly thereto,

each of the floating sulpho groups on the naphthalene components, independently, is in the 3- or 4-position, which complexes are free from fibre reactive groups and are in free acid or salt form, and mixtures of such complexes.

It will be appreciated that the coupling component radicals B₁ and B₂ must bear one or more substituents which activate coupling for example, hydroxy and primary, secondary and tertiary amino groups (preferably only one hydroxy group). Preferred amino groups are --NH₂ and phenylamino in which the phenyl nucleus is optionally substituted by (C₁₋₄)alkyl. Preferably, the coupling component radicals bear not more than two such activating groups. In addition to such activating substituents it will be appreciated that the coupling component radicals may be further substituted by substituents common for coupling components in anionic disazo dyes. Preferably, each of the coupling component radicals, independently, is optionally further substituted by an alkyl (preferably C₁₋₄)) or alkoxy (preferably (C₁₋₄)) group or by a halogen atom. Preferably, each of B₁ and B₂ is independently 8-hydroxyquinolyl or substituted phenyl having one or two substituents selected from hydroxy, --NH₂, phenylamino (anilino) and (C₁₋₄)alkylphenylamino, with the proviso that not more than one substituent is selected from phenylamino and (C₁₋₄)alkylphenylamino, and, optionally, one further substituent selected from halo, (C₁₋₄)alkyl and (C₁₋₄)alkoxy. More preferably, when any of B₁ and B₂ is substituted phenyl, it has one or two substituents selected from --NH₂ and hydroxy (maximum of one hydroxy) and, optionally, one further substituent selected from halo, (C₁₋₄)alkyl and (C₁₋₄)alkoxy.

It will be appreciated that the rings A₁ and A₂ may bear substituents which are common for diazo components of the benzene series. Preferably, each of rings A₁ and A₂, independently, is unsubstituted or substituted by up to two substituents selected from the group consisting of halogen, nitro, (C₁₋₄)alkyl, (C₁₋₄)alkoxy and --SO₂ NR₁ R₂ (at most one --SO₂ NR₁ R₂ group), in which R₁ is hydrogen or (C₁₋₄)alkyl, and R₂ is hydrogen, (C₁₋₄)alkyl or ##STR5## wherein R₃ is hydrogen, halogen, (C₁₋₄)alkyl, (C₁₋₄)-alkoxy or --COOH. Preferably, the ring A₁ and/or A₂ bears a maximum of one halogen atom and/or a maximum of one group selected from (C₁₋₄)alkyl and (C₁₋₄)alkoxy.

By halogen as used herein is meant chlorine, bromine, fluorine or iodine.

Any alkyl or alkoxy group on rings A₁ and/or A₂ or on the coupling component radicals B₁ and/or B₂ preferably contains 1 or 2 carbon atoms with methyl and methoxy being especially preferred.

Any halogen on rings A₁ and/or A₂ or on the coupling component radicals B₁ and/or B₂ is preferably chlorine or bromine, especially chlorine.

R₁ is preferably R₁ ', where R₁ ' is hydrogen or methyl, more preferably hydrogen.

R₃ is preferably R₃ ', where R₃ ' is hydrogen, chlorine, methyl, methoxy or carboxy, more preferably R₃ is R₃ ", where R₃ " is hydrogen or carboxy.

R₂ is preferably R₂ ', where R₂ ' is hydrogen, methyl or ##STR6## More preferably R₂ is R₂ ", where R₂ " is methyl or ##STR7##

Preferably, each of the radicals ##STR8## independently, is a radical of formula A_(x), ##STR9## in which Q₁ is hydrogen or nitro, and

Q₂ is hydrogen, chlorine, nitro or --SO₂ --NR₁ R₂, more preferably

Q₂ is hydrogen, chlorine, nitro or SO₂ NR₁ 'R₂ '.

Preferably, Q₁ is hydrogen when Q₂ is --SO₂ NR₁ R₂. More preferably, each of the radicals ##STR10## independently, is a radical of formula A_(x) ' in which A_(x) ' is a group of formula A_(x) wherein Q₂ is chlorine, nitro or --SO₂ NR₁ 'R₂ ', more preferably chlorine, nitro or --SO₂ NHR₂ ", with the proviso that where Q₂ is an aminosulphonyl group Q₁ is hydrogen.

Preferably, each of the coupling component radicals B₁ and B₂, independently, is of formula (a), (b) or (c) ##STR11## in which Y₁ is --NH₂ or --OH,

Y₂ is --NH₂ or ##STR12## Y₃ is hydrogen, (C₁₋₄)alkyl, (C₁₋₄)alkoxy or chlorine, wherein when Y₃ is other than hydrogen, it is in a position ortho or para to Y₁, and

Y₄ is hydrogen or (C₁₋₄)alkyl.

When

Y₂ is ##STR13## Y₁ is preferably hydroxy and Y₃ is preferably hydrogen. The substituent Y₄ may be in any position but is preferably in the 2- or 4-position, with the 2-position being most preferred.

Y₃ is preferably hydrogen or (C₁₋₄)alkyl, especially hydrogen or methyl.

More preferably (a) is (a'), ##STR14## in which R₄ is hydrogen or methyl.

Of the coupling component radicals of formulae (a), (b) and (c), those of formulae (a) and (b) are preferred, with those of formula (a'), especially those of formula (a') where R₄ is hydrogen, being most preferred.

The floating sulpho group on each of the the naphthalene nuclei is preferably bound to the 3-position.

Each of X₁ and X₂ is preferably --O--.

Preferred complexes of formula I are those in which each of the rings A₁ and A₂, independently, is unsubstituted or substituted by a total of up to two substituents selected from the group consisting of halogen, nitro, (C₁₋₄)alkyl, (C₁₋₄)alkoxy and --SO₂ NR₁ R₂ (at most one --SO₂ NR₁ R₂ group), and each of the coupling component radicals B₁ and B₂, independently, is a radical of formula (a), (b) or (c), preferably (a) or (b) and especially (a'). Of these preferred complexes, those wherein each of X₁ and X₂ is --O-- are preferred, with those wherein X₁ and X₂ are both --O-- and the floating sulpho groups are in the 3-positions of the naphthalene nuclei being particularly preferred.

Of these preferred complexes, those wherein each of the rings A₁ and A₂, independently, is unsubstituted or substituted by a total of up to two substituents selected from the group consisting of nitro, --SO₂ NR₁ R₂ (a maximum of one --SO₂ NR₁ R₂ group), halogen atoms (a maximum of one halogen atom), (C₁₋₄)alkyl and (C₁₋₄)alkoxy (a maximum of either one alkyl or one alkoxy group) and preferably, when any of the rings A₁ and A₂ bears a --SO₂ NR₁ R₂ group, such ring bears no further substituent, with those compounds where each of B₁ and B₂, independently, is a radical of formula (a) or (b), especially (a), being most preferred.

More preferred complexes of formula I are those of formula I', ##STR15## in which each of B₁ and B₂, independently, is a radical of formula (a') and A_(x) is as defined above. Preferably, in the groups of formula A_(x), Q₁ is hydrogen when Q₂ is --SO₂ NR₁ R₂.

Of the complexes of formula I', the complexes wherein each A_(x), independently, is A_(x) ' are more preferred, with those wherein B₁ and B₂ are 2,4-diaminophenyl being even more preferred. Of the complexes of these two groups, those wherein any --SO₂ NR₁ 'R₂ ' as Q₂ is --SO₂ NHR₂ " are even more preferred.

Of the complexes of formulae I and I', the symmetrical complexes are preferred, especially those wherein B₁ and B₂ are 2,4-diaminophenyl.

When the complexes of formula I are in salt form the cations of the salt form of the acid groups may be any of those which are common for anionic metallic complexes. Preferred cations are alkali metal cations, especially sodium, lithium or potassium, unsubstituted ammonium, (C₁₋₄), preferably (C₁₋₂),alkyl-substituted ammonium or hydroxy(C₂₋₄) preferably (C₂₋₃)substituted-ammonium. The unsubstituted, lower alkyl substituted and hydroxyalkyl substituted ammonium cations may be represented by the formula --N.sup.⊕ (R_(x))₄, where each R_(x) is, independently, hydrogen, (C₁₋₄)alkyl or 2-, 3- or 4-hydroxy(C₂₋₄)alkyl, with the proviso that when any R_(x) is hydroxyalkyl at least one other R_(x) is hydrogen. Examples of such cations are ammonium, triethylammonium, mono-, di- and triethanolammonium and mono-, di- and triisopropanolammonium.

By "salt form" is intended those complexes wherein all or part of the sulpho groups are in salt form and optionally any carboxyl groups present are in salt form. It will be appreciated that when the complexes of the present invention are in salt form, the protons compensating the negative charge of the chromium may, to a greater or lesser extent, depending on the conditions employed, be replaced by the cations of the salt form of the acid groups.

Preferably, the complexes of formula I are in salt form.

The present invention also provides a process for the production of complexes of formula I comprising coupling the bisdiazo derivative of a complex of formula II, ##STR16##

which complex is in free acid or salt form, or a mixture of complexes of formula II, with a coupling component H-B₁, or a mixture thereof, and with a coupling component H-B₂, or a mixture thereof.

The complexes of formula II may be produced by treating the compounds of formulae V and VI, or mixtures of those compounds, ##STR17##

with a chromium-donating compound in accordance with known methods.

Metallization may be carried out in accordance with conventional methods, either by first forming a 1:1 complex of a compound of formula V or VI and reacting the same with a compound of formula VI or V, respectively, or by simultaneously metallizing the compounds of formulae V and VI.

Diazotization and coupling may be carried out in accordance with known methods. Coupling is preferably carried out in a medium having a pH of from 4 to 13. The complexes of formula I may be isolated in conventional manner.

The compounds of formulae V and VI are either known or may be prepared from available starting materials in accordance with known methods, for example by diazotizing a compound of the formula ##STR18## and coupling with 1-amino-8-hydroxynaphthalene-3- or 4-,6-disulphonic acid or a salt thereof.

The complexes of formula I and the mixtures thereof are useful for dyeing or printing substrates dyeable with anionic dyestuffs. Preferred substrates are those which consist of or comprise natural or regenerated cellulose, natural or synthetic polymides, leather, polyurethanes and basically modified polymers such as, for example, basically modified polypropylene, which substrates may be in the form of fibres, filaments, yarns, wovens, felts, fleeces, carpets, halffinished or finished goods. More preferred substrates are synthetic polyamides, wool and especially leather. The leather may be tanned in the usual manner, e.g. naturally, synthetically and/or chrome tanned. Dyeing or printing may be carried out in accordance with known methods for example, by exhaust dyeing, pad dyeing or printing. The dyestuff may be employed in concentrations up to the saturation point of the substrate, for example, 0.001 to 1% or 0.01 to 5% pure dyestuff.

The complexes of formula I and the mixtures thereof may be employed as such or may be used in the form of liquid or solid preparations which are obtained in accordance with known methods by combining the dyestuff with blending agents and other conventional additives.

The grey dyes of the present invention have good build-up on leather of low affinity and give even dyeings on leather having good fastnesses, especially light fastness. Also to be mentioned are rubbing fastness and fastness to perspiration, water and dry-cleaning.

The following Examples further serve to illustrate the invention. In the Examples all parts and percentages are by weight and the temperatures are in degrees Centigrade.

EXAMPLE 1

199 parts of 2-amino-4,6-dinitro-1-hydroxybenzene are diazotised in the usual manner with hydrochloric acid and sodium nitrite and are coupled at a pH of 7-9 with 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid. The monoazo compound thus obtained is heated to 100° C. and then 120 parts of chromium acetate are added. The mixture is boiled at 100° C. (about 2-4 hours) until the monoazo compound has completely reacted to form the 1:2 chromium complex. The 1:2 chromium complex is subsequently diazotised in the usual manner with hydrochloric acid and sodium nitrite and coupled at a pH of 9-13 with 145 parts of 8-hydroxyquinoline. The dyestuff obtained is precipitated with common salt. It is a black powder which dyes leather in grey shades.

EXAMPLE 2

Following the procedure of Example 1, but employing, instead of the 145 parts of 8-hydroxyquinoline, 108 parts of m-diaminobenzene and coupling at a pH of 5-9, a dyestuff, which is a black powder and dyes leather in grey shades, is obtained.

In the above Examples 1 and 2 the alkaline pH for the coupling is obtained by employing lithium, sodium, potassium or ammonium hydroxide and thus, the dyestuffs are obtained in the corresponding salt forms.

The following table contains further Examples of dyestuffs according to the invention. These dyestuffs in the free acid form correspond to the general formula ##STR19##

and may be produced in analogy with the procedure described in Examples 1 and 2.

                                      Table                                        __________________________________________________________________________     Example                         Shade of dyeing                                No.  Z.sub.1      Z.sub.2                                                                            B         on leather                                     __________________________________________________________________________     3    NO.sub.2     NO.sub.2                                                                            ##STR20##                                                                               bluish-grey                                    4    NO.sub.2     NO.sub.2                                                                            ##STR21##                                                                               "                                              5    NO.sub.2     NO.sub.2                                                                            ##STR22##                                                                               greenish-grey                                  6    SO.sub.2 NH . CH.sub.3                                                                      H                                                                                   ##STR23##                                                                               neutral grey                                   7    "            "                                                                                   ##STR24##                                                                               "                                                    ##STR25##   "                                                                                   ##STR26##                                                                               "                                              9    "            "                                                                                   ##STR27##                                                                               "                                              10   "            "                                                                                   ##STR28##                                                                               "                                                                     ##STR29##                                               11   NO.sub.2     H                                                                                   ##STR30##                                                                               grey                                           12   "            "                                                                                   ##STR31##                                                                               bluish-grey                                    13   "            "                                                                                   ##STR32##                                                                               greenish-grey                                  14   Cl           "                                                                                   ##STR33##                                                                               neutral grey                                   15   "            "                                                                                   ##STR34##                                                                               bluish-grey                                    16   NO.sub.2     "                                                                                   ##STR35##                                                                               greenish grey                                  17   Cl           H                                                                                   ##STR36##                                                                               greenish-grey                                  18   Cl           NO.sub.2                                                                           "         "                                              19   SO.sub.2NHCH.sub.3                                                                          H   "         neutral grey                                   20                                                                                   ##STR37##   H   "         "                                              21                                                                                   ##STR38##   H   "         "                                              22   SO.sub.2 NH.sub.2                                                                           H   "         "                                              __________________________________________________________________________

Application Example A

100 parts of newly tanned and neutralised chromium grain leather are milled for 30 minutes in a dye vessel in a liquor consisting of 250 parts of water at 55° and 0.5 parts of the dyestuff of Example 1; the leather is then treated in the same bath for a further 30 minutes with 2 parts of an anionic fat-liquor based on sulphonated train oil. The leather is dried and finished in the usual manner. An even dyeing in a grey shade is obtained.

Application Example B

100 parts of calf suede are milled in a dye vessel for 4 hours with 1000 parts of water and 2 parts of ammonia and are subsequently dyed for 11/2 hours in a further bath containing: 500 parts of water at 55°, 2 parts of ammonia, 5 parts of dissolved dyestuff of Example 1. In order to exhaust the dyebath, 4 parts of formic acid (85%) are slowly added and dyeing continues until the dyestuff has been completely fixed. After buffing the suede side, the suede leather which is rinsed, dried and finished in the usual manner is evenly dyed in a grey shade.

Application Example C

100 parts of chromium-vegetable tanned lamb's leather and 5 parts of the dyestuff of Example 1 are milled for 45 minutes in a dye vessel, in a liquor consisting of 1000 parts of water at 55° and 1.5 parts of an anionic sperm oil emulsion, and the dyestuff is fixed on the leather by slowly adding 5 parts of formic acid (85%) over the course of 30 minutes. After the usual drying and finishing processes, an even dyeing of a grey shade is obtained.

Application Example D

A solution of 20 parts of the dyestuff of Example 1 in 847 parts of water, 150 parts of ethyl glycol and 3 parts of formic acid (85%) is applied by spraying, plushing and pouring to the grain side of a buffed, combined-tanned cow-hide.

The leather is dried and finished under mild conditions. A dyeing of a grey shade with good fastnesses is obtained.

In analogous manner to the procedure described in the above Examples A-D, the dyestuffs of Examples 2-22 may be used, whereby even dyeings of shades indicated in the Table are obtained. 

What is claimed is:
 1. A complex of the formula ##STR39## or a salt thereof, or a mixture of such complexes in free acid or salt form, whereineach of ##STR40## is independently the radical of a diazo component of the benzene series, with the proviso that rings A₁ and A₂ are free from acid groups bound directly thereto and free from fiber-reactive groups, each of B₁ and B₂ is independently 8-hydroxyquinolyl or substituted phenyl having (i) one or two substituents each of which is independently hydroxy, --NH₂, anilino or (C₁₋₄ alkyl)phenylamino, with the proviso that not more than one substituent is selected from anilino and (C₁₋₄ alkyl)phenylamino, and (ii) a maximum of one substituent selected from the group consisting of C₁₋₄ alkyl, C₁₋₄ alkoxy and halo, each of X₁ and X₂ is independently --O-- or --COO--, and each of the sulfo groups on rings C and D is independently in the 3- or 4-position,wherein each halo is independently fluoro, chloro, bromo or iodo.
 2. A complex according to claim 1, or a salt thereof, or a mixture of such complexes in free acid or salt form,wherein each of rings A₁ and A₂ is independently further unsubstituted or further substituted by one or two substituents each of which is independently halo, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy or --SO₂ NR₁ R₂, with the proviso that the maximum number of --SO₂ NR₁ R₂ substituents is one, wherein R₁ is hydrogen or C₁₋₄ alkyl, and R₂ is hydrogen, C₁₋₄ alkyl or ##STR41## wherein R₃ is hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy or carboxy.
 3. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein ##STR42## are identical, B₁ and B₂ are identical, X₁ and X₂ are identical, and the sulfo groups on rings C and D are both in the 3-position or both in the 4-position.
 4. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of B₁ and B₂ is independently substituted phenyl having (i) one or two substituents each of which is independently hydroxy, --NH₂, anilino or (C₁₋₄ alkyl)phenylamino, with the proviso that not more than one substituent is selected from anilino and (C₁₋₄ alkyl)phenylamino, and (ii) a maximum of one substituent selected from the group consisting of C₁₋₄ alkyl, C₁₋₄ alkoxy and halo.
 5. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein R₁ is hydrogen or methyl, and R₂ is hydrogen, methyl or ##STR43## wherein R₃ ' is hydrogen, chloro, methyl, methoxy or carboxy.
 6. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of ##STR44## wherein Q₁ is hydrogen or nitro, and Q₂ is hydrogen, chloro, nitro or --SO₂ NR₁ R₂,wherein R₁ is hydrogen or C₁₋₄ alkyl, and R₂ is hydrogen, C₁₋₄ alkyl or ##STR45## wherein R₃ is hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy or carboxy, with the proviso that Q₁ must be hydrogen when Q₂ is --SO₂ NR₁ R₂.
 7. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of B₁ and B₂ is independently 8-hydroxyquinolyl or substituted phenyl having (i) one or two substituents each of which is independently --NH₂ or hydroxy, with the proviso that not more than one substituent is hydroxy, and (ii) a maximum of one substituent selected from the group consisting of C₁₋₄ alkyl, C₁₋₄ alkoxy and halo.
 8. A complex according to claim 2, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of B₁ and B₂ is independently ##STR46## wherein Y₁ is --NH₂ or hydroxy, Y₂ is --NH₂, anilino or (C₁₋₄ alkyl)-phenylamino, and Y₃ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or chloro, with the proviso that when Y₃ is C₁₋₄ alkyl, C₁₋₄ alkoxy or chloro and is attached to a ring having a Y₁ substituent, it is ortho or para to Y₁.
 9. A complex according to claim 8, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of B₁ and B₂ is independently ##STR47##
 10. A complex according to claim 9, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each of B₁ and B₂ is independently ##STR48## wherein R₄ is hydrogen or methyl.
 11. A complex according to claim 8, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein X₁ is --O--, and X₂ is --O--.
 12. A complex according to claim 11 having the formula ##STR49## or a salt thereof, or a mixture of such complexes in free acid or salt form,wherein each of B₁ ' and B₂ ' is independently ##STR50## wherein R₄ is hydrogen or methyl, each Q₁ is independently hydrogen or nitro, and each Q₂ is independently hydrogen, chloro, nitro or --SO₂ NR₁ R₂, wherein R₁ is hydrogen or C₁₋₄ alkyl, and R₂ is hydrogen, C₁₋₄ alkyl ##STR51## wherein R₃ is hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy or carboxy, with the proviso that Q₁ must be hydrogen when Q₂ is --SO₂ NR₁ R₂,wherein each halo is independently fluoro, chloro, bromo or iodo.
 13. A complex according to claim 12, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein each Q₂ is independently chloro, nitro or --SO₂ NR₁ 'R₂ ', wherein R₁ ' is hydrogen or methyl, and R₂ ' is hydrogen, methyl or ##STR52## wherein R₃ ' is hydrogen, methyl, methoxy, chloro or carboxy.
 14. A complex according to claim 13, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein R₁ ' is hydrogen, and R₂ ' is methyl, phenyl or carboxyphenyl.
 15. A complex according to claim 14, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein B₁ ' is 2,4-diaminophenyl, and B₂ ' is 2,4-diaminophenyl.
 16. A complex according to claim 12, or a salt thereof,or a mixture of such complexes in free acid or salt form, wherein B₁ ' and B₂ ' are identical, and the two ##STR53## radicals are identical.
 17. The complex according to claim 16 having the formula ##STR54## or a salt thereof.
 18. The complex according to claim 16 having the formula ##STR55## or a salt thereof.
 19. The complex according to claim 16 having the formula ##STR56## or a salt thereof.
 20. The complex according to claim 16 having the formula ##STR57## or a salt thereof.
 21. The complex according to claim 16 having the formula ##STR58## or a salt thereof. 